Manganese complexes of salen ligands and the use thereof

ABSTRACT

The present invention relates to novel manganese complexes of salen ligands and the use thereof as catalysts that enhance the action of peroxy compounds in washing, cleaning, and disinfecting processes.

The present invention relates to novel manganese complexes of salenligands and to the use thereof as catalysts that enhance the action ofperoxy compounds in washing, cleaning and disinfecting processes. Theinvention furthermore relates to formulations used in such processesthat comprise the manganese complexes and peroxy compounds, and also tothe novel ligands and to processes for the preparation thereof.

A number of manganese complexes of the salen type are already known tobe suitable catalysts for oxidations that use peroxy compounds,especially within the context of washing procedures. Also, certain othermanganese complexes have already been described as having a pronouncedbleaching action on dirt and dyes in washing liquors. There isnevertheless still a need for further compounds having improved actionand/or a broader field of application, but such compounds should notcause any appreciable damage to fibres or colours when used on textilematerial.

It has now been found that certain novel manganese complexes of thesalen type as catalysts largely meet the required conditions. Theyenhance the action of peroxy compounds in a very wide variety ofapplications, substantially without damage occurring to fibres orcolours. Surprisingly, when the manganese complexes according to theinvention are employed in aqueous solution together with peroxycompounds, the enhanceed action occurs in the following applications:

a) the bleaching of stains or soiled areas on textile material withinthe context of a washing procedure,

b) the inhibition of migrating dyes being redeposited when textilematerial is washed,

c) the cleaning of hard surfaces, especially crockery or glass,

d) the cleaning of hard surfaces, especially glazed tiles or floortiles, especially for the removal of stains that have formed as a resultof the action of molds (mold stains), and

e) the use of washing and cleaning solutions that have an antibacterialactivity.

The present invention accordingly relates to compounds of formula

wherein

n is 0, 1 or 2,

m is 1 or 2,

A is an anion;

Y is a linear or branched alkylene radical of formula —[C(R₅)₂]_(r)—wherein r is an integer of from 1 to 8 and the R₅ radicals are eachindependently of the others hydrogen or C₁-C₄alkyl; —CX═CX— wherein X iscyano, linear or branched C₁-C₈alkyl or di(linear or branchedC₁-C₈alkyl)amino; —(CH₂)_(q)—NR₄—(CH₂)_(q)— wherein R₄ is hydrogen orC₁-C₄alkyl and q is 1, 2, 3or 4; or

a 1,2-cyclohexylene radical of formula:

 or a 1,2-aryl radical of formula

 wherein R₉ is hydrogen, SO₃H, CH₂OH or CH₂NH₂,

R and R₁ are each independently of the other nitro, NR₆R₇ wherein R₆ ishydrogen or linear or branched C₁-C₁₂alkyl and R₇ is linear or branchedC₁-C₁₂alkyl, with the proviso that R₆ and R₇ in the groups NR₆R₇ are notidentical, or —CH₂—N^(⊕)R₄R₆R₇ or —N^(⊕)R₄R₆R₇ wherein R₄, R₆ and R₇ areas defined above,

R₂ and R₃ are each independently of the other hydrogen, linear orbranched C₁-C₄alkyl, unsubstituted aryl, or aryl substituted by cyano;by halogen; by OR₅ or COOR₅ wherein R₅ is hydrogen or linear or branchedC₁-C₄alkyl; by nitro; by linear or branched C₁-C₈alkyl; by NHR₆ or NR₆R₇wherein R₆ and R₇ are identical or different and are each linear orbranched C₁-C₁₂alkyl; by linear or branched C₁-C₈alkyl-R₈ wherein R₈ isa radical OR₅, COOR₅ or NR₆R₇ as defined above or is NH₂; or by—N^(⊕)R₄R₆R₇ wherein R₄, R₆ and R₇ are as defined above,

and, when n and m are each 1, R₂ and R₃ are each hydrogen and Y isunsubstituted 1,2-cyclohexylene, R and R₁ are not each nitro in the 5-and 5′-position, respectively, and, when n and m are each 1, R₂ and R₃are each hydrogen and Y is unsubstituted 1,2-ethylene, R and R₁ are noteach N^(⊕)(CH₃)(C₂H₅)₂ in the 4- and 4′-position, respectively.

In compounds of formula (1) in which n is 2, the radicals R may haveidentical or different meanings. The same applies to compounds offormula (1) in which m is 2 in respect of the radicals R₁.

When Y is a 1,2-cyclohexylene radical, that radical may be in either ofits stereoisomeric cis/trans forms.

Preferably, Y is a cyclohexylene radical, a radical of formula(CH₂)_(r)— wherein r is an integer of from 1 to 8, or a radical offormula —C(R₅)₂—(CH₂)_(p)—C(R₅)₂— wherein p is an integer of from 0 to 6and R₅ is hydrogen or C₁-C₄alkyl.

In especially preferred compounds of formula (1), Y is a cyclohexyleneradical, a radical of formula —(CH₂)_(r)— wherein r is an integer offrom 1 to 4, or a radical of formula —(CR₅)₂—(CR₅)₂— wherein the R₅radicals are each independently of the others hydrogen or methyl.

Halogen is preferably chlorine, bromine or fluorine, chlorine beingespecially preferred.

When n or m is 1, the groups R and R₁ are preferably in the 4- or5-position of the respective benzene ring.

When R₆ or R₇ is an alkyl radical, the alkyl group may be straight-chainor branched. Preferably, the alkyl group contains from 1 to 8,especially from 1 to 4, and more especially from 1 to 3, carbon atoms.

Preferably, the radicals R and R₁ are each nitro, NR₆R₇ wherein R₆ andR₇ are each C₁-C₄alkyl, with the proviso that R₆ and R₇ are notidentical, or —N^(⊕)R₄R₆R₇ wherein R₄, R₆ and R₇ are each C₁-C₄alkyl.

The radicals R₂ and R₃ are especially hydrogen, methyl, ethyl, orunsubstituted phenyl.

Aryl is, for example, naphthyl or, especially, phenyl.

Suitable anions include, for example, halide, for example chloride,bromide or iodide, perchlorate, sulfate, nitrate, hydroxide, BF₄ ⁻, PF₆⁻, carboxylate, acetate, tosylate and triflate. Of those, preference isgiven to chloride, bromide, iodide and acetate.

The compounds of formula (1) are prepared, for example, in a mannerknown per se from the corresponding ligands and a manganese compound.Preparation processes of that kind are described, for example, in U.S.Pat. Nos. 5,281,578 and 4,066,459.

The ligands of formula

wherein R, R₁, R₂, R₃, Y, n and m are as defined for formula (1) arelikewise novel. They are prepared in a manner known per se, for exampleby reacting a diamine of formula H₂N—Y—NH₂ first of all with an aldehydeor ketone of formula

and then with an aldehyde or ketone of formula

In formulae (3) and (4), R, R₁, R₂, R₃, n and m are as defined forformula (1). When, in the compounds of formula (2), (R)_(n) has the samemeaning as (R₁)_(m) and R₂ has the same meaning as R₃ then, for thesynthesis of compounds of formula (2), one mol of a diamine of formulaH₂N—Y—NH₂ is reacted with two mols of an aldehyde or ketone of formula(3).

The diamines of formula H₂N—Y—NH₂ and the aldehydes or ketones offormula (3) and (4) are known or can be prepared in a manner known perse.

The compounds of formula (1) are used as catalysts for oxidations usingperoxy compounds, for example for bleaching textile material, withoutcausing appreciable damage to fibres and colours.

The present invention accordingly further relates to a washing andcleaning process which comprises adding to the liquor, which comprises aperoxide-containing washing and cleaning agent, from 0.1 to 200 μmol ofone or more compounds of formula (1) per liter of washing liquor.

The present invention relates also to a method of inhibiting theredeposition of migrating dyes present in a washing liquor, whichcomprises adding to the washing liquor, which comprises aperoxide-containing washing agent, from 0.5 to 150 mg, preferably from1.5 to 75 mg, especially from 7.5 to 40 mg, of one or more compounds offormula (1) per liter of washing liquor.

The present invention relates furthermore to a washing agent containing

I) from 5 to 90%, preferably from 5 to 70%, A) of an anionic surfactantand/or B) of a non-ionic surfactant,

II) from 5 to 70%, preferably from 5 to 50%, especially from 5 to 40%,C) of a builder substance,

III) from 0.1 to 30%, preferably from 1 to 12%, D) of a peroxide and

IV) from 0.005 to 2%, preferably from 0.02 to 1%, especially from 0.1 to0.5%, E) of a compound of the above-defined formula (1), the percentagesin each case being percentages by weight, based on the total weight ofthe washing agent.

The washing agent may be in solid or liquid form, for example in theform of a liquid, non-aqueous washing agent containing not more that 5%,preferably from 0 to 1%, by weight of water, and may comprise as base asuspension of a builder substance in a non-ionic surfactant, for exampleas described in GB-A-2 158 454.

The washing agent is preferably, however, in the form of a powder orgranules.

The powder or granules can be prepared, for example, by first preparinga starting powder by spray-drying an aqueous suspension comprising allof the above-listed components with the exception of components D) andE), and then adding the dry components D) and E) and mixing everythingtogether.

It is also possible to add component E) to an aqueous suspensioncomprising components A), B) and C), then subject the mixture tospray-drying and subsequently mix component D) with the dry mass.

It is furthermore possible to start with an aqueous suspension thatcomprises components A) and C) but not component B) or only a proportionof component B). The suspension is spray-dried and then component E) ismixed with component B) and added, and subsequently component D) isadmixed dry.

The anionic surfactant A) may be, for example, a sulfate, sulfonate orcarboxylate surfactant or a mixture of such surfactants.

Preferred sulfates are those having from 12 to 22 carbon atoms in thealkyl radical, if desired in combination with alkylethoxysulfates inwhich the alkyl radical contains from 10 to 20 carbon atoms.

Preferred sulfonates include, for example, alkylbenzenesulfonates havingfrom 9 to 15 carbon atoms in the alkyl radical.

The cation in the anionic surfactants is preferably an alkali metalcation, especially sodium.

Preferred carboxylates are alkali metal sarcosinates of formulaR—CO—N(R¹)—CH₂COOM¹, wherein R is alkyl or alkenyl having from 8 to 18carbon atoms in the alkyl or alkenyl radical, R¹ is C₁-C₄alkyl and M¹ isan alkali metal.

The non-ionic surfactant B) may be, for example, a condensation productof from 3 to 8 mols of ethylene oxide with 1 mol of primary alcohol thatcontains from 9 to 15 carbon atoms.

Suitable builder substances C) include, e.g., alkali metal phosphates,especially tripolyphosphates, carbonates or bicarbonates, especially thesodium salts thereof, silicates, aluminium silicates, polycarboxylates,polycarboxylic acids, organic phosphonates,aminoalkylenepoly(alkylenephosphonates) and mixtures of such compounds.

Silicates that are especially suitable are sodium salts of crystallinelayer silicates of formula NaHSi_(t)O₂₁₊₁.pH₂O or Na₂Si_(t)O₂₁₊₁.pH₂O,wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.

Of the aluminium silicates, preference is given to those obtainablecommercially under the names zeolite A, B, X and HS and to mixtures thatcomprise two or more of those components.

Of the polycarboxylates, preference is given to thepolyhydroxycarboxylates, especially citrates, and acrylates and alsocopolymers thereof with maleic anhydride.

Preferred polycarboxylic acids are nitrilotriacetic acid,ethylenediaminetetraacetic acid and ethylenediamine disuccinate both inracemic form and the enantiomerically pure S,S-form.

Especially suitable phosphonates oraminoalkylenepoly(alkylenephosphonates) include alkali metal salts of1-hydroxyethane-1,1-diphosphonic acid, nitrilo-tris(methylenephosphonicacid), ethylenediaminetetramethylenephosphonic acid anddiethylenetriaminepenta-methylenephosphonic acid.

Suitable peroxide components D) include, for example, the organic andinorganic peroxides known in the literature and available commerciallythat bleach textile materials at conventional washing temperatures, forexample at from 10 to 95° C.

The organic peroxides are, for example, mono- or poly-peroxides,especially organic peracids or salts thereof, such asphthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioicacid, diperoxynonanedioic acid, diperoxydecanedioic acid,diperoxyphthalic acid or salts thereof.

Preference is given, however, to the use of inorganic peroxides, suchas, for example, persulfates, perborates, percarbonates and/orpersilicates. It will be understood that it is also possible to usemixtures of inorganic and/or organic peroxides. The peroxides can bepresent in various crystalline forms and with various water contents,and they can also be used together with other inorganic or organiccompounds for the purpose of improving their storage stability.

The addition of the peroxides to the washing agent is carried outpreferably by mixing the components together, for example using a screwmetering system and/or a fluidized bed mixer.

The washing agent may comprise, in addition to the combination accordingto the invention, one or more optical brighteners, for example from thegroup comprising bistriazinylamino-stilbenedisulfonic acid,bistdazolylstilbenedisulfonic acid, bisstyrylbiphenyl orbisbenzofuranylbiphenyl, a bisbenzoxalyl derivative, bisbenzimidazolylderivative, coumarin derivative or a pyrazoline derivative.

The washing agents may furthermore comprise suspending agents for dirt,for example sodium carboxymethylcellulose, pH regulators, e.g. alkalimetal or alkaline earth metal silicates, foam regulators, e.g. soap,salts for regulating the spray-drying and the granulating properties,e.g. sodium sulfate, perfumes and, optionally, antistatic agents andsofteners, enzymes, such as amylase, bleaching agents, pigments and/ortoning agents. It will be understood that such components must be stablewith respect to the bleaching agent used.

Further preferred additives to the washing agents according to theinvention are polymers that, when textile materials are being washed,inhibit staining caused by dyes in the washing liquor that have beenreleased from the textile materials under the washing conditions. Suchpolymers are preferably polyvinylpyrrolidones which, as appropriate, mayhave been modified by the incorporation of anionic or cationicsubstituents, especially those having a molecular weight in the rangefrom 5000 to 60 000, more especially from 10 000 to 50 000. Suchpolymers are used preferably in an amount of from 0.05 to 5% by weight,especially from 0.2 to 1.7% by weight, based on the total weight of thewashing agent.

In addition, the washing agents according to the invention may alsocomprise so-called perborate activators, such as, for example, TAED orTAGU. Preference is given to TAED, which is preferably used in an amountof from 0.05 to 5% by weight, especially from 0.2 to 1.7% by weight,based on the total weight of the washing agent.

Surprisingly, the manganese complexes of formula (1) also have amarkedly improved bleach-catalyzing action on coloured stains on hardsurfaces. The addition of such complexes in catalytic amounts to adishwashing agent that comprises a peroxy compound and optionally TAED(N,N,N′,N′-tetraacetylethylenediamine) results in the substantialremoval of tea stains from porcelain at 45° C. in automatic dishwashers.This is the case even when hard water is used, it being known that teadeposits are more difficult to remove in hard water than in soft water.

The invention accordingly relates also to the use of manganese complexesof formula (1) as catalysts for reactions with peroxy compounds incleaning solutions for hard surfaces, especially for crockery.

The invention relates furthermore to cleaning agents for hard surfaces,especially cleaning agents for crockery and, among such agents,preferably those for use in cleaning processes carried out by machine,which agents comprise one of the above-described compounds of formula(1) as bleach catalyst, and to a method of cleaning hard surfaces,especially crockery, using such a bleach catalyst.

The manganese complexes of formula (1) according to the invention arefurthermore excellently suitable for cleaning hard surfaces, especiallyglazed tiles or floor tiles, especially for the removal of stains thathave formed as a result of the action of molds (“mold stains”). Suchstains frequently occur in the joints between glazed tiles. The jointsmay consist, for example, of cement-containing and/or gypsum-containingmaterial, or of polymers, for example silicone.

The invention accordingly relates also to the use of manganese complexesof formula (1) as catalysts for reactions with peroxy compounds incleaning solutions for glazed tiles and floor tiles, or the jointsbetween such tiles, and to the cleaning solutions used for that purposecomprising a manganese complex of formula (1) and a peroxide andoptionally further additives, such as, for example, surfactants.

Used together with peroxy compounds, the manganese complexes of formula(1) according to the invention furthermore exhibit excellentantibacterial activity. The invention relates also to the use of themanganese complexes of formula (1) according to the invention to killbacteria or to provide protection against attack by bacteria.

The following Examples serve to illustrate the invention without theinvention being limited thereto. Parts and percentages relate to weight,unless specified otherwise. Preparation of the ligands is expedientlycarried out under an argon atmosphere.

EXAMPLE 1 N,N′-Bis(4-trimethylammoniumsalicylidene)-1,2-ethylenediaminedihydrobromide

55 mg (0.915 mmol) of ethylenediamine are added dropwise, at 50° C., toa suspension of 500 mg (1.92 mmol) of4-formyl-3-hydroxyphenyltrimethylammonium bromide [directions forsynthesis: M. Ando, S. Emoto, Bull. Chem. Soc. Jpn., Vol. 42 (9) 2624(1969)] in 2 ml of ethanol. The reaction mixture is maintained at 80° C.for 4 hours. After cooling to room temperature, the precipitate formedis filtered off, washed with a small amount of cold ethanol and dried toconstant weight under a high vacuum at 40° C.

Yield: 390 mg (78%), yellowish solid. ¹³C NMR (DMSO-d₆) δ=57.1 (NCH₃),58.4 (NCH₂), 110.6,134.2 (tert. aryl-C), 119.7, 150.9, 163.7 (quat.aryl-C), 167.0 (C═N).

EXAMPLE 2 N,N′-Bis(5-trimethylammoniumsalicylidene)-1,2-ethylenediaminedihydrobromide

Synthesis and working up are carried out as in Example 1, starting from500 mg (1.92 mmol) of 3-formyl4-hydroxyphenyltrimethylammonium bromide[directions for synthesis: M. Ando and S. Emoto, Bull. Chem. Soc. Jpn.,Vol. 51 (8) 2433 (1978)].

Yield: 492 mg (99%), yellowish solid. ¹³C NMR (DMSO-d₆) δ=57.3 (NCH₃),58.2 (NCH₂), 119.7, 124.5, 125.7 (tert. aryl-C), 118.2, 138.1, 163.6(quat. aryl-C), 166.8 (C═N).

EXAMPLE 3(R,R)-N,N′-Bis(5-trimethylammoniumsalicylidene)-1,2-cyclohexanediaminedihydrobromide

Synthesis and working up are carried out as in Example 1, starting from500 mg (1.92 mmol) of 3-formyl4-hydroxyphenyltrimethylammonium bromideand 0.105 g (0.915 mmol) of trans-1,2-diaminocyclohexane.

Yield: 435 mg (79%), yellowish solid. ¹³C NMR (DMSO-d₆) δ=19.8, 25.527.4, 29.2 (cycl. CH₂), 53.4 (NCH₃), 63.6 (CH₂—CH), 118.7,121.9, 123.1(tert. aryl-C), 111.4, 131.5, 172.4 (quat. aryl-C), 163.2 (C═N).

EXAMPLE 4(R,R)-N,N′-Bis(4-trimethylammoniumsalicylidene)-1,2-cyclohexanediaminedihydrobromide

Synthesis and working up are carried out as in Example 1, starting from500 mg (1.92 mmol) of 4-formyl-3-hydroxyphenyltrimethylammonium bromideand 0.105 g (0.915 mmol) of trans-1,2-diaminocyclohexane.

Yield: 299 mg (55%), yellowish-beige solid. ¹³C NMR (D₂O) δ=23.6, 29.5,31.3, 33.1 (cycl. CH₂), 56.8 (NCH₃), 67.3 (CH₂—CH), 107.5, 112.0, 136.1(tert. aryl-C), 117.3, 152.4, 170.9 (quat. aryl-C), 166.6 (C═N).

EXAMPLE 5N,N′-Bis(5-trimethyiammoniumsalicylidene)-2-methylpropane-1,2-diaminedihydrobromide

Synthesis and working up are carried out as in Example 1, starting from500 mg (1.92 mmol) of 3-formyl-4-hydroxyphenyltrimethylammonium bromideand 81 mg (0.915 mmol) of 1,2-diamino-2-methylpropane.

Yield: 425.6 mg (81%), yellowish solid. ¹³C NMR (D₂O) δ=23.7 (CH₃), 57.3(NCH₃), 60.0 ((CH₃)₂ C), 64.2 (NCH₂), 119.7, 124.5, 125.7,135.2 (tert.aryl-C), 117, 137.2, 164.4 (quat. aryl-C), 164.5, 168.7 (C═N).

EXAMPLE 6N,N′-Bis(5-trimethylammoniumsalicylidene)-2-methylpropane-1,2-diaminedihydrobromide

Synthesis and working up are carried out as in Example 1, starting from500 mg (1.92 mmol) of 4-formyl-3-hydroxyphenyltrimethylammonium bromideand 81 mg (0.915 mmol) of 1,2-diamino-2-methylpropane.

Yield: 369 mg (70%), lemon-yellow solid. ¹³C NMR (DMSO-d₆) δ=24.8 (CH₃),56.1 (NCH₃), 60.1 ((CH₃)₂—C), 67.9 (NCH₂), 109.5, 109.7, 109.8, 133.2,133.6 (tert. aryl-C), 118.9, 150.0, 162.1, 163.2 (quat. aryl-C), 162.4,166.4 (C═N).

EXAMPLE 7 4-(N-Ethyl-N-methylamino)salicylaldehyde

6.14 g (0.066 mol) of phosphorus oxychloride are cautiously added to 19ml of dry DMF at −5° C. within a period of 5 minutes, during the courseof which the temperature of the reaction solution should not exceed 10°C. Subsequently, a solution of 9.9 g (0.066 mol) of3-(N-ethyl-N-methylamino)phenol in 14 ml of dry DMF is added theretowithin a period of 10 minutes, during the course of which thetemperature of the reaction solution should not exceed 20° C. When theaddition is complete, the reaction solution is heated for 2 hours at 90°C. and then immediately poured onto 100 g of ice. The crude mixture isstirred for 30 minutes. The reaction solution is extracted three timeswith 100 ml of chloroform. The combined organic phases are concentratedunder a high vacuum. The oily residue which remains is purified bycolumn chromatography on silica gel (eluant n-hexanelchloroform 95:5).Yield: 5.8 g (26%), colourless solid.

¹H NMR (CDCl₃) δ=1.19 (m, 3H, CH ₃—CH₂), 3.03 (s, 3H, NCH₃), 3.45 (m,2H, CH₃—CH ₂), 6.08 (s, 1H, aryl-H), 6.29, 7.30 (m, each 1H, aryl-H),9.05 (s, 1H, CH═O), 11.62 (s, 1H, OH). ¹³C NMR (CDCl₃) δ=11.8 (CH₃—CH₂),37.7 (NCH₃), 46.8 (CH₃—CH₂), 97.0, 104.5, 135.3 (tert. aryl-C), 111.6,155.2, 164.2 (quat. aryl-C), 192.1 (C═O).

EXAMPLE 8 4-(N-Isopropyl-N-methylamino)salicylaldehyde

11 g (0.118 mol) of phosphorus oxychloride are cautiously added to 33 mlof dry DMF at −5° C. within a period of 5 minutes, during the course ofwhich the temperature of the reaction solution should not exceed 10° C.Subsequently, a solution of 19.4 g (0.1176 mol) of3-(N-isopropyl-N-methylamino)phenol in 25 ml of dry DMF is added theretowithin a period of 10 minutes, during the course of which thetemperature of the reaction solution should not exceed 20° C. When theaddition is complete, the reaction solution is heated for 2 hours at 90°C. and then immediately poured onto 150 g of ice. The crude mixture isextracted three times with 100 ml of chloroform. The combined organicphases are concentrated under a high vacuum. The oily residue ispurified by column chromatography on silica gel (eluantn-hexane/chloroform 95:5). Yield: 5.8 g (26%), colourless liquid.

¹H NMR (CDCl₃) δ=1.21 (m, 6H, (CH ₃)₂—CH), 2.87 (s, 3H, NCH₃), 4.18 (m,(CH₃)₂—CH), 6.18 (s, 1H, aryl-H), 6.38, 7.27 (m, each 1H, aryl-H), 9.51(s, 1H, CH═O), 11.59 (s, 1H, OH). ¹³C NMR (CDCl₃) δ=19.7 ((CH₃)₂CH),30.1 (NCH₃), 48.6 ((CH₃)₂—CH), 97.3, 104.8, 135.2 (tert. aryl-C), 111.6,155.9, 164.3 (quat. aryl-C), 192.0 (C═O).

EXAMPLE 9N,N′-Bis[4-(N-ethyl-N-methylamino)salicylidene]-1,2-ethylenediamine

A solution of 80 mg (1.33 mmol) of ethylenediamine is added dropwise, atroom temperature, to a solution of 500 mg (2.79 mmol) of4-(N-ethyl-N-methylamino)salicylaldehyde and the reaction solution isheated for 4 hours at 70° C. After cooling to room temperature, theprecipitate formed is filtered off, washed with a small amount of coldethanol and dried in a vacuum drying cabinet at 30° C.

Yield: 476 mg (94%), yellow solid. ¹H NMR (CDCl₃) δ=1.13 (m, 6H, CH₃—CH₂), 2.92 (s, 6H, NCH₃), 3.38 (m, 4H, CH₃—CH ₂), 3.76 (s, 4H, NCH₂),6.12 (m, 4H, aryl-H), 6.98 (m, 2H, aryl-H), 8.08 (s, 2H, CH═N), 13.52(s, br, 2H, OH). ¹³C NMR (CDCl₃) δ=11.7 (CH₃—CH₂), 37.4 (NCH₃), 46.6(CH₃—CH₂), 58.4 (NCH₂), 68.8 (NCH₂),98.6,103.3,132.8 (tert. aryl-C),108.6,152.6,165.4 (quat. aryl-C), 164.6 (C═N).

EXAMPLE 10N,N′-Bis[4-(N-isopropyl-N-methylamino)salicylidene]-1,2-ethylenediamine

Synthesis and working up are carried out as in Example 9, starting from500 mg (2.59 mmol) of 4-(N-isopropyl-N-methylamino)salicylaldehyde and90 mg (1.5 mmol) of ethylenediamine.

Yield: 429 mg (81%), yellow solid. ¹H NMR (CDCl₃) δ=1.17 (m, 12H, (CH₃)₂—CH), 2.78 (s, 6H, NCH₃), 3.38 (m, 4H, CH₃—CH ₂), 3.74 (s, 4H, NCH₂),4.12 (m, 2H, (CH₃)₂—CH), 6.19 (m, 4H, aryl-H), 6.95 (m, 2H, aryl-H),8.05 (s, 2H, CH═N), 13.52 (s, br, 2H, OH). ¹³C NMR (CDCl₃) δ=19.6(CH₃—CH), 29.8 (NCH—(CH₃)₂), 48.3 (NCH₃), 46.6 (CH₃—CH₂), 58.5 (NCH₂),99.1, 103.7, 132.7 (tert. aryl-C), 108.7, 153.5, 165.2 (quat. aryl-C),164.5 (C═N).

EXAMPLE 11(R,R)N,N′-Bis[4-(N-isopropyl-N-methylamino)salicylidene]-1,2-cyclohexanediamine

Synthesis and working up are carried out as in Example 9, starting from500 mg (2.59 mmol) of 4-(N-isopropyl-N-methylamino)salicylaldehyde and141 mg (1.23 mmol) of trans-1,2-cyclohexanediamine. Yield: 504 mg (88%),yellow solid.

¹H NMR (CDCl₃) δ=1.18 (m, 12H, (CH ₃)₂—CH), 1.41, 1.65, 1.83, 1.95 (m,each CH₂), 2.72 (s, 6H, NCH₃), 3.17 (m, 2H, cyc. CH), 4.10 (m, 2H,(CH₃)₂—CH), 6.15 (m, 4H, aryl-H), 6.90 (m, 2H, aryl-H), 7.95 (s, 2H,CH═N), 13.8 (s, 2H, OH). ¹³C NMR (CDCl₃) δ=19.6 (CH₃), 24.3, 33.2 (CH₂),29.8 ((CH₃)—CH), 48.2 (NCH₃), 71.0 (cycl. CH), 99.2, 103.6, 103.8, 132.8(tert. aryl-C), 108.7, 153.4, 165.5 (quat. aryl-C), 162.9 (C═N).

EXAMPLE 12 (R,R)-N,N′-Bis[4-(N-ethyl-N-methylamino)salicylidene]-1,2-cyclohexanediamine

Synthesis and working up are carried out as in Example 9, starting from500 mg (2.79 mmol) of 4-(N-ethyl-N-methylamino)salicylaldehyde and 152mg (1.33 mmol) of trans-1,2-cyclohexanediamine. Yield: 569 mg (98%),yellow solid.

¹H NMR (CDCl₃) δ=1.10 (m, 6H, (CH ₃), 1.40, 1.61, 1.80, 1.93 (m, each2H, CH₂), 2.88 (s, 6H, NCH₃), 3.10 (cycl. CH), 3.37 (m, 4H, NCH₂), 6.05(m, 4H, aryl-H), 6.88 (m, 2H, aryl-H), 7.93 (m, 2H, CH═N), 13.2 (s, br,2H, OH). ¹³C NMR (CDCl₃) δ=11.6 (CH₃), 24.3, 33.2 (cycl. CH₂), 37.6(NCH₃), 46.5 (CH₃ CH₂), 70.8 (cycl. CH), 98.6, 103.2, 132.9 (tert.aryl-C), 108.5, 152.5, 165.9 (quat. aryl-C), 162.9 (C═N).

EXAMPLE 13N,N′-Bis[4-(N-ethyl-N-methylamino)salicylidene]-2-methylpropane-1,2-diamine

Synthesis and working up are carried out as in Example 9, starting from500 mg (2.79 mmol) of 4-(ethylmethylamino)salicylaldehyde and 117 mg(1.33 mmol) of 1,2-diamino-2-methylpropane.

Yield: 518. mg (95%), yellowish solid. ¹³C NMR (CDCl₃) δ=11.7, 25.4(CH₃), 37.5 (NCH₃), 46.6 (CH₃ CH₂), 58.6 (C(CH₃)₂), 68.9 (NCH₂), 98.7,99.1, 103.3, 133.0, 133.2 (tert. aryl-C), 108.6, 152.7, 153.0, 165.7,167.8 (quat. aryl-C), 159.2, 164.7 (C═N).

EXAMPLE 14N,N′-Bis[4-(N-isopropyl-N-methylamino)salicylidene]-2-methylpropane-1,2-diamine

Synthesis and working up are carried out as in Example 9, starting from500 mg (2.59 mmol) of 4-(N-isopropyl-N-methylamino)salicylaldehyde and109 mg (1.23 mmol) of 1,2-diamino-2-methylpropane.

Yield: 524 mg (97%), yellowish oil. ¹³C NMR (CDCl₃) δ=19.7, 25.4, 29.8(CH₃), 48.2 (NCH₃), 58.6 (N—C(CH₃)₂—), 68.8 (NCH₂), 99.1, 99.6, 103.7,103.8, 132.8, 133.1 (tert. aryl-C), 108.7, 153.6, 153.9, 165.7, 167.8,(quat. aryl-C), 159.1, 164.6 (C═N).

EXAMPLE 15 N,N′-Bis(4-nitrosalicylidene)-1,2-ethylenediamine

4 ml of methanol are added to a solution of 500 mg (2.99 mmol) of4-nitrosalicylaldehyde (for preparation see Beilstein E IV, Vol. 8, 232)in 2 ml of ethanol. 95.2 mg (106 μl, 1.58 mmol) of ethylenediamine areadded dropwise to the resulting yellow suspension. The reactionsuspension is heated for 4 hours at 70° C. After cooling to roomtemperature, the precipitate formed is filtered off, washed with 2 ml ofethanol and dried to constant weight under a high vacuum at 30° C.

Yield: 488.1 mg, orange solid. ¹³C NMR (DMSO-d₆) δ=58.0 (NCH₂), 111.5,123.3, 132.6 (tert. aryl-C), 149.5, 161.4 (quat. aryl-C), 165.6 (C═N).

The synthesis of the manganese(III)-salen complexes from the describedsalen ligands can be carried out in two ways: in known manner or in situby the addition of Mn(II) salts in methanolic solution.

EXAMPLE 16[(R,R)-N,N′-Bis(4-(N-isopropyl-N-methylamino)salicylidene)-1,2-cyclohexanediaminato]-manganese(III)chloride

111 mg (0.452 mmol) of manganese(II) acetate tetrahydrate are added to asolution of 210 mg (0.452 mmol) of ligand from Example 11 in 9 ml ofethanol. The suspension is stirred for 8 hours at room temperature andthen heated for 4 hours at 70° C. The resulting dark-red solution isconcentrated under a high vacuum. The solid which remains is taken up in9 ml of distilled water and 500 mg of sodium chloride are added. Theprecipitate formed is filtered off, washed with a small amount of coldwater and dried under a high vacuum at 30° C.

Yield: 250 mg (quantitative), reddish-brown solid.

EXAMPLE 17(R,R)-N,N′-Bis(5-(triethylammoniomethylsalicylidene)-1,2-cyclohexanediaminedihydrochloride

1.09 g (4 mmol) of (5-triethylammoniomethyl)salicylaldehyde chloride(for synthesis see T. Tanaka et al., Bull. Chem. Soc. Jpn. 1997, 70,615-629) are dissolved in 10 ml of water and 0.228 g (2 mmol) of1,2-diaminocyclohexane dissolved in 2 ml of water is added thereto. Theyellow solution is stirred at room temperature for 2 hours and thenconcentrated at 60° C. bath temperature (10 mbar) using a rotaryevaporator. 50 ml of tetrahydrofuran are added twice, followed each timeby concentration. 1.22 g of the desired product are obtained in the formof yellow crystals of >90% purity (NMR).

¹³C NMR (D₂O): δ=7.4 (CH₃), 23.8, 31.3, 52.3, 59.6 (aliph. CH₂), 67.7(tert. C), 115.0, 116.5 (quat. aryl-C), 121.5, 138.5, 139.4 (tert.aryl-C), 166.9 (C═N), 171.5 (quat. aryl-C).

EXAMPLE 18N,N′-Bis(5-(triethylammoniomethylsalicylidene)-1,2-ethanediaminedihydrochloride

The compound is synthesised analogously to the directions given inExample 17. Yellow crystals of >90% purity (NMR) are obtained.

¹³C NMR (D₂O) δ=7.4 (CH₃), 52.2, 53.5, 59.6 (in each case aliph. CH₂),114.6,116.4 (quat. aryl-C), 120.5, 138.9, 139.6 (tert. aryl-C), 168.7(C═N), 172.3 (quat. aryl-C).

EXAMPLE 19 Use of the Salen Complexes as DTI Catalysts

In order to examine the activity of the catalysts, the DTI activity isascertained. The DTI (dye transfer inhibition) activity a is defined asthe following percentage:

a=([Y(E)−Y(A)]/[Y(W)−Y(A)]) ×100

wherein Y(W), Y(A) and Y(E) denote the CIE brightness values of thewhite material, of the material treated without the addition of catalystand of the material treated with the addition of catalyst, in thatorder. a=0 denotes a completely unusable product, which when added tothe washing liquor allows the dye transfer to proceed freely. a=100%, onthe other hand, corresponds to a perfect catalyst, which completelyprohibits staining of the white material by dye.

In order to ascertain the test data, the following test system is used:7.5 g of white cotton fabric are treated in 80 ml of washing liquor. Theliquor contains the standard washing agent ECE phosphate-free (456 IEC)EMPA, Switzerland, in a concentration of 7.5 g/l, 8.6 mmol/l H₂O₂ and asolution of the test dye. The washing process is carried out in a beakerin a LINITEST apparatus for 30 min. at 40° C. The catalyst is added inthe concentration indicated in each case.

Commercially available Direct Brown 172 (dye 1) with 10 mg/l of the 250%formulation or Reactive Blue 238 (dye 2) with 6 mg/l of the 100%formulation are used as test dyes. The reflection spectra of thespecimens are measured using a SPECTRAFLASH 2000 and converted bystandard CIE procedure into brightness values (D65/10).

Table 1 shows the very good DTI effects a(%) of the complexes accordingto the invention. The concentration of catalysts used in the washingliquor is in each case 50 μmol/l (exception: the catalyst from Example10: 15 μmol/l). The conditions of use are as described hereinabove.

TABLE 1 Manganese complex of the DTI effect a (%) ligands from ExampleDye 1 Dye 2 1 89 90 2 93 88 3 88 92 4 91 92 5 84 89 6 87 93 9 91 94 1088 90 11 86 89 12 87 85 13 85 85 14 88 87 15 89 91 16 90 85

EXAMPLE 20 Use of the Salen Complexes as Bleach Catalysts for Crockery

This Example illustrates the action of the manganese complexes of theligands from Examples 3 and 6 as catalysts for peroxy compounds forcleaning tea-stained porcelain cups in an automatic dishwasher.

Staining Procedure

A tea brew (12 g of tea-leaves/liter) is prepared from black tea(Twinings brand) and hard water (total hardness: 18° dH) by stirring at99° C. The tea brew is left to draw for five minutes and the tea isfiltered. Approximately 100 ml of tea are then poured into a porcelaincup. The tea is left to stand in the cups for 30 minutes. The cups arethen emptied in three steps each of approximately 35 ml. A period offive minutes is left between the emptying steps. The completely emptycups are dried for 60 minutes at 70° C.

Dishwashing Agent

A phosphate-containing base formulation (without oxygen bleaching agentand without TAED) having the following composition is used.

Constituents % by weight sodium tripolyphosphate 30-60 sodium carbonate20-30 hydrated 2.0 r silicate  5-20 non-ionic surfactant 0.5-5  protease 0.5-5   amylase 0.5-5   bentonite 1-5

Cleaning Procedure

The cups are cleaned in a Miele G-690 D dishwasher on the delicateprogramme at 45° C. using hard water. In each cleaning programme 12tea-stained cups are cleaned. The machine also contains six glasses withmilk stains, 24 clean plates and 60 g of a mixture of various foodstuffs(for example spinach, egg, starch etc.). The dishwashing agentcomprises: 17.2 g of the phosphate-containing base formulation, 1.72 gof sodium perborate-monohydrate, 0.8 g of TAED. As appropriate, 100 ppmof catalyst (ppm based on the metal) are added to the cleaning liquor.After the cleaning operation, the removal of the tea deposit isevaluated visually on a scale from 0 (=unchanged, very strong deposit)to 10 (=no deposit). Table 2 shows the ratings for our catalystscompared with a reference (TAED only no catalyst). The ratings indicatedin Table 2 are the median values from several cleaning programmes eachusing 12 cups. The Table shows that the ratings for the catalystsaccording to the invention are significantly better than the referencevalue.

TABLE 2 Ratings for removal of the deposit Catalyst from Example RatingReference (TAED only, no catalyst) 1 3 7.5 6 8.5

What is claimed is:
 1. A compound of formula

wherein n is 1 or 2, m is 1 or 2, A is an anion; Y is a linear orbranched alkylene radical of formula —[C(R₅)₂]_(r)— wherein r is aninteger of from 1 to 8 and the R₅ radicals are each independently of theothers hydrogen or C₁-C₄alkyl; —CX═CX— wherein X is cyano, linear orbranched C₁-C₈alkyl or di(linear or branched C₁-C₈alkyl)amino;—(CH₂)_(q)—NR₄—(CH₂)_(q)— wherein R₄ is hydrogen or C₁-C₄alkyl and q is1, 2, 3 or 4; or a 1,2-cyclohexylene radical of formula:

 or a 1,2-aryl radical of formula

 wherein R₉ is hydrogen, SO₃H, CH₂OH or CH₂NH₂, R and R₁ are eachindependently of the other nitro, NR₆R₇ wherein R₆ is linear or branchedC₁-C₁₂alkyl and R₇ is linear or branched C₁-C₁₂alkyl, with the provisothat R₆ and R₇ in the groups NR₆R₇ are not identical, or—CH₂—N^(⊕)R₄R₆R₇ or —N^(⊕)R₄R₆R₇ wherein R₄, R₆ and R₇ are as definedabove, R₂ and R₃ are each independently of the other hydrogen, linear orbranched C₁-C₄alkyl, unsubstituted aryl, or aryl substituted by cyano;by halogen; by OR₅ or COOR₅ wherein R₅ is hydrogen or linear or branchedC₁-C₄alkyl; by nitro; by linear or branched C₁-C₈alkyl; by NHR₆ orNR₆R₇wherein R₆ and R₇ are identical or different and are each linear orbranched C₁-C₁₂alkyl; by linear or branched C₁-C₈alkyl-R₈ wherein R₈ isa radical OR₅, COOR₅ or NR₆R₇ as defined above or is NH₂; or by—N^(⊕)R₄R₆R₇ wherein R₄, R₆ and R₇ are as defined above, and, when n andm are each 1, R₂ and R₃ are each hydrogen and Y is unsubstituted1,2-cyclohexylene, R and R₁ are not each nitro in the 5- and5′-position, respectively, and, when n and m are each 1, R₂ and R₃ areeach hydrogen and Y is unsubstituted 1,2-ethylene, R and R₁ are not eachN^(⊕)(CH₃)(C₂H₅)₂ in the 4- and 4′-position, respectively.
 2. A compoundaccording to claim 1, wherein Y is a cyclohexylene radical, a radical offormula —(CH₂)_(r)— wherein r is an integer of from 1 to 4, or a radicalof formula —C(R₅)₂—C(R₅)₂— wherein the R₅ radicals are eachindependently of the others hydrogen or methyl.
 3. A compound accordingto claim 1, wherein the groups R and R₁ are in the 4- or 5-position ofthe respective benzene ring.
 4. A compound according to claim 1, whereinthe radicals R and R₁ are each nitro, NR₆R₇ in which R₆ and R₇ are eachC₁-C₄alkyl, with the proviso that R₆ and R₇ are not identical, or—N^(⊕)R₄R₆R₇ in which R₄, R₆ and R₇ are each C₁-C₄alkyl.
 5. A compoundaccording to claim 1, wherein the radicals R₂ and R₃ are each hydrogen,methyl, ethyl, or unsubstituted phenyl.
 6. A compound according to claim1, wherein the anion A is chloride, bromide, iodide or acetate.
 7. Amethod of inhibiting the redeposition of migrating dyes present in awashing liquor, which comprises adding to the washing liquor, whichcomprises a peroxide-containing washing agent, from 0.5 to 150 mg of oneor more compounds of formula (1) according to claim 1 per liter ofwashing liquor.
 8. A washing agent containing I) from 5 to 90% A) of ananionic surfactant and/or B) of a non-ionic surfactant, II) from 5 to70% C) of a builder substance, III) from 0.1 to 30% D) of a peroxide andIV) from 0.005 to 2% E) of a compound of formula (1) according to claim1, the percentages in each case being percentages by weight, based onthe total weight of the washing agent.
 9. A cleaning agent for hardsurfaces, comprising a compound of formula (1) according to claim 1 asbleach catalyst and a peroxy compound.
 10. A cleaning agent for glazedtiles and floor tiles, or joints between such tiles, comprising acompound of formula (1) according to claim 1 as bleach catalyst and aperoxy compound and also, optionally, further additives.
 11. A washingagent containing I) from 5 to 70% A) of an anionic surfactant and/or B)of a non-ionic surfactant, II) from 5 to 50% C) of a builder substance,III) from 1 to 12% D) of a peroxide and IV) from 0.02 to 1% E) of acompound of formula (1) according to claim 1, the percentages in eachcase being percentages by weight, based on the total weight of thewashing agent.
 12. A method to kill bacteria or to provide protectionagainst attack by bacteria, which comprises contacting said bacteriawith a solution containing a peroxy compound and a manganese complex offormula (1) according to claim 1 as catalyst for the reaction of theperoxy compound.